Polymer Composition and Film for Use in 5G Applications

ABSTRACT

A polymer composition comprising a liquid crystalline polymer that contains repeating units derived from naphthenic hydroxycarboxylic and/or dicarboxylic acids in an amount of about 50 mol. % or more is provided. The polymer composition exhibits a dielectric constant of about 4 or less and a dissipation factor of about 0.05 or less at a frequency of 10 GHz.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application claims filing benefit of U.S. Provisional PatentApplication Ser. No. 62/898,188 having a filing date of Sep. 10, 2019;U.S. Provisional Patent Application Ser. No. 62/904,089 having a filingdate of Sep. 23, 2019; U.S. Provisional Patent Application Ser. No.62/986,072 having a filing date of Mar. 6, 2020; U.S. Provisional PatentApplication Ser. No. 62/994,321 having a filing date of Mar. 25, 2020;U.S. Provisional Patent Application Ser. No. 63/008,989 having a filingdate of Apr. 13, 2020; and U.S. Provisional Patent Application Ser. No.63/024,596 having a filing date of May 14, 2020, which are incorporatedherein by reference in their entirety.

BACKGROUND OF THE INVENTION

Flexible printed circuit boards are routinely employed in high density,small electronic components. Such circuit boards are typically producedfrom a “copper clad laminate” that contains an insulative polymer filmand a copper foil from which the circuit paths are etched.Unfortunately, however, problems have occurred in attempting to useconventional printed circuit boards in 5G applications. Moreparticularly, transmitting and receiving at the high frequenciesencountered in a 5G application generally results in an increased amountof power consumption and heat generation. As a result, the materialsoften used to form the insulative film in conventional printed circuitboards can negatively impact high frequency performance capabilities. Assuch, a need exists for films for use in 5G antenna systems.

SUMMARY OF THE INVENTION

In accordance with one embodiment of the present invention, a polymercomposition is disclosed that comprises a liquid crystalline polymerthat contains repeating units derived from naphthenic hydroxycarboxylicand/or dicarboxylic acids in an amount of about 50 mol. % or more. Thepolymer composition exhibits a dielectric constant of about 4 or lessand a dissipation factor of about 0.05 or less at a frequency of 10 GHz.Further, the polymer composition exhibits a tensile elongation of about2% or more as determined at a temperature of about 23° C. in accordancewith ISO Test No. 527:2012.

In accordance with another embodiment of the present invention, a filmis disclosed that comprises a polymer composition. The polymercomposition comprises a liquid crystalline polymer that containsrepeating units derived from 6-hydroxy-2-naphthoic acid in an amount ofabout 70 mol. % or more. The polymer composition exhibits a dielectricconstant of about 4 or less and a dissipation factor of about 0.05 orless at a frequency of 10 GHz.

Other features and aspects of the present invention are set forth ingreater detail below.

BRIEF DESCRIPTION OF THE FIGURES

A full and enabling disclosure of the present invention, including thebest mode thereof to one skilled in the art, is set forth moreparticularly in the remainder of the specification, including referenceto the accompanying figures, in which:

FIG. 1 depicts one embodiment of a 5G antenna system that can employed acircuit board formed according to the present invention;

FIG. 2A illustrates a top-down view of an example user computing deviceincluding 5G antennas;

FIG. 2B illustrates a side elevation view of the example user computingdevice of FIG. 2A;

FIG. 3 illustrates an enlarged view of a portion of the user computingdevice of FIG. 2A;

FIG. 4 illustrates a side elevation view of co-planar waveguide antennaarray configuration that can be employed in a 5G antenna system;

FIG. 5A illustrates an antenna array for massivemultiple-in-multiple-out configurations of a 5G antenna system;

FIG. 5B illustrates an antenna array formed that can be employed in a 5Gantenna system;

FIG. 5C illustrates an example antenna configuration that can beemployed in a 5G antenna system;

FIG. 6 is a schematic view of one embodiment a laminate that can beformed according to the present invention;

FIG. 7 is a schematic view of another embodiment a laminate that can beformed according to the present invention;

FIG. 8 is a schematic view of yet another embodiment a laminate that canbe formed according to the present invention; and

FIG. 9 is a schematic view of one embodiment of an electronic devicethat may be employ the circuit board of the present invention.

DETAILED DESCRIPTION

It is to be understood by one of ordinary skill in the art that thepresent discussion is a description of exemplary embodiments only, andis not intended as limiting the broader aspects of the presentinvention.

Generally speaking, the present invention is directed to a polymercomposition for use in films that are well-suited for 5G applications.The polymer composition contains a liquid crystalline polymer. Byselectively controlling the particular nature of the liquid crystallinepolymer and other aspects of the composition, the present inventors havediscovered that the resulting composition can exhibit a low dielectricconstant and dissipation factor over a wide range of frequencies. Thatis, the polymer composition may exhibit a low dielectric constant ofabout 4 or less, in some embodiments about 3.6 or less, in someembodiments from about 0.1 to about 3.5, and in some embodiments, fromabout 1 to about 3.4 over typical 5G frequencies (e.g., 2 or 10 GHz).The dissipation factor of the polymer composition, which is a measure ofthe loss rate of energy, may likewise be about 0.05 or less, in someembodiments about 0.01 or less, in some embodiments from about 0.0001 toabout 0.008, and in some embodiments from about 0.0002 to about 0.006over typical 5G frequencies (e.g., 2 or 10 GHz). In fact, in some cases,the dissipation factor may be very low, such as about 0.003 or less, insome embodiments about 0.002 or less, in some embodiments about 0.001 orless, in some embodiments, about 0.0009 or less, in some embodimentsabout 0.0008 or less, and in some embodiments, from about 0.0001 toabout 0.0007 over typical 5G frequencies (e.g., 2 or 10 GHz).

Conventionally, it was believed that polymer compositions exhibiting alow dissipation factor and dielectric constant would not also possesssufficiently good mechanical properties to enable its use in films.Contrary to conventional thought, however, the polymer composition hasbeen found to possess both excellent properties. Notably, the polymercomposition may exhibit a tensile elongation of about 2% or more, insome embodiments about 3% or more, in some embodiments from about 4% toabout 15%, and in some embodiments from about 5% to about 12%, such asdetermined at a temperature of about 23° C. in accordance with ISO TestNo. 527:2012. Such high tensile elongation properties have been found tobe useful in achieving good elongation properties for a resulting film.Of course, the polymer composition may also possess other goodmechanical properties. For example, the polymer composition may exhibita tensile strength of about 10 MPa or more, in some embodiments about 50MPa or more, in some embodiments from about 100 MPa to about 300 MPa,and in some embodiments from about 120 MPa to about 200 MPa and/or atensile modulus of about 20,000 MPa or less, in some embodiments about15,000 MPa or less, and in some embodiments, from about 3,500 MPa toabout 10,000 MPa, such as determined at a temperature of about 23° C. inaccordance with ISO Test No. 527:2012. Also, the polymer composition mayexhibit a flexural strength of about 20 MPa or more, in some embodimentsabout 30 MPa or more, in some embodiments about 50 MPa or more, in someembodiments from about 90 MPa to about 300 MPa, and in some embodimentsfrom about 100 MPa to about 250 MPa; flexural elongation of about 0.5%or more, in some embodiments from about 1% to about 15%, and in someembodiments from about 2% to about 12%; and/or a flexural modulus ofabout 20,000 MPa or less, in some embodiments about 15,000 MPa or less,and in some embodiments, from about 4,000 MPa to about 13,000 MPa. Theflexural properties may be determined at a temperature of about 23° C.in accordance with 178:2010. Furthermore, the polymer composition mayalso possess a high impact strength, which may be useful when formingthin films. The polymer composition may, for instance, possess a Charpynotched impact strength of about 1 kJ/m² or more, in some embodimentsabout 5 kJ/m² or more, in some embodiments about 15 kJ/m² or more, insome embodiments from about 20 kJ/m² to about 150 kJ/m², and in someembodiments from about 40 kJ/m² to about 120 kJ/m². The impact strengthmay be determined at a temperature of 23° C. in accordance with ISO TestNo. ISO 179-1:2010.

The polymer composition may also exhibit excellent thermal properties.For example, the melting temperature of the polymer composition may, forinstance, be about 200° C. to about 400° C., in some embodiments fromabout 250° C. to about 380° C., in some embodiments from about 280° C.to about 360° C., in some embodiments from about 290° C. to about 350°C., and in some embodiments, from about 300° C. to about 340° C. Even atsuch melting temperatures, the ratio of the deflection temperature underload (“DTUL”), a measure of short term heat resistance, to the meltingtemperature may still remain relatively high. For example, the ratio mayrange from about 0.5 to about 1.00, in some embodiments from about 0.6to about 0.95, and in some embodiments from about 0.65 to about 0.85.The specific DTUL values may, for instance, be about 150° C. or more, insome embodiments from about 160° C. to about 350° C., in someembodiments from about 170° C. to about 340° C., and in some embodimentsfrom about 180° C. to about 320° C. Such high DTUL values can, amongother things, allow the use of high speed and reliable surface mountingprocesses for mating the structure with other components of anelectrical component.

Various embodiments of the present invention will now be described inmore detail.

I. Polymer Composition

A. Liquid Crystalline Polymer

Liquid crystalline polymers are generally classified as “thermotropic”to the extent that they can possess a rod-like structure and exhibit acrystalline behavior in their molten state (e.g., thermotropic nematicstate). The liquid crystalline polymers employed in the polymercomposition typically have a melting temperature of from about 200° C.to about 400° C., in some embodiments from about 250° C. to about 380°C., in some embodiments from about 280° C. to about 360° C., in someembodiments from about 290° C. to about 350° C., and in someembodiments, from about 300° C. to about 340° C. The melting temperaturemay be determined as is well known in the art using differentialscanning calorimetry (“DSC”), such as determined by ISO Test No.11357-3:2011. Such polymers may be formed from one or more types ofrepeating units as is known in the art. A liquid crystalline polymermay, for example, contain one or more aromatic ester repeating unitsgenerally represented by the following Formula (I):

wherein,

ring B is a substituted or unsubstituted 6-membered aryl group (e.g.,1,4-phenylene or 1,3-phenylene), a substituted or unsubstituted6-membered aryl group fused to a substituted or unsubstituted 5- or6-membered aryl group (e.g., 2,6-naphthalene), or a substituted orunsubstituted 6-membered aryl group linked to a substituted orunsubstituted 5- or 6-membered aryl group (e.g., 4,4-biphenylene); and

Y₁ and Y₂ are independently O, C(O), NH, C(O)HN, or NHC(O).

Typically, at least one of Y₁ and Y₂ are C(O). Examples of such aromaticester repeating units may include, for instance, aromatic dicarboxylicrepeating units (Y₁ and Y₂ in Formula I are C(O)), aromatichydroxycarboxylic repeating units (Y₁ is O and Y₂ is C(O) in Formula I),as well as various combinations thereof.

Aromatic hydroxycarboxylic repeating units, for instance, may beemployed that are derived from aromatic hydroxycarboxylic acids, suchas, 4-hydroxybenzoic acid; 4-hydroxy-4′-biphenylcarboxylic acid;2-hydroxy-6-naphthoic acid; 2-hydroxy-5-naphthoic acid;3-hydroxy-2-naphthoic acid; 2-hydroxy-3-naphthoic acid;4′-hydroxyphenyl-4-benzoic acid; 3′-hydroxyphenyl-4-benzoic acid;4′-hydroxyphenyl-3-benzoic acid, etc., as well as alkyl, alkoxy, aryland halogen substituents thereof, and combination thereof. Particularlysuitable aromatic hydroxycarboxylic acid repeating units are thosederived from 4-hydroxybenzoic acid (“HBA”) and 6-hydroxy-2-naphthoicacid (“HNA”) as set forth below in Formula II and Ill, respectively:

Aromatic dicarboxylic repeating units may also be employed that arederived from aromatic dicarboxylic acids, such as terephthalic acid,isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenylether-4,4′-dicarboxylic acid, 1,6-naphthalenedicarboxylic acid,2,7-naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl,bis(4-carboxyphenyl)ether, bis(4-carboxyphenyl)butane,bis(4-carboxyphenyl)ethane, bis(3-carboxyphenyl)ether,bis(3-carboxyphenyl)ethane, etc., as well as alkyl, alkoxy, aryl andhalogen substituents thereof, and combinations thereof. Particularlysuitable aromatic dicarboxylic acid repeating units include thosederived from terephthalic acid (“TA”), isophthalic acid (“IA”), or2,6-naphthalenedicarboxylic acid (“NDA”) as set forth below in FormulaIV, V, and VI, respectively:

Other repeating units may also be employed in the polymer. In certainembodiments, for instance, repeating units may be employed that arederived from aromatic diols, such as hydroquinone, resorcinol,2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene,1,6-dihydroxynaphthalene, 4,4′-dihydroxybiphenyl (or 4,4′-biphenol),3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, 4,4′-dihydroxybiphenylether, bis(4-hydroxyphenyl)ethane, etc., as well as alkyl, alkoxy, aryland halogen substituents thereof, and combinations thereof. Particularlysuitable aromatic diol repeating units are those derived fromhydroquinone (“HQ”) or 4,4′-biphenol (“BP”). Repeating units may also beemployed, such as those derived from aromatic amides (e.g.,acetaminophen (“APAP”)) and/or aromatic amines (e.g., 4-aminophenol(“AP”), 3-aminophenol, 1,4-phenylenediamine, 1,3-phenylenediamine,etc.). It should also be understood that various other monomericrepeating units may be incorporated into the polymer. For instance, incertain embodiments, the polymer may contain one or more repeating unitsderived from non-aromatic monomers, such as aliphatic or cycloaliphatichydroxycarboxylic acids, dicarboxylic acids, diols, amides, amines, etc.Of course, in other embodiments, the polymer may be “wholly aromatic” inthat it lacks repeating units derived from non-aromatic (e.g., aliphaticor cycloaliphatic) monomers.

Regardless of the particular repeating units employed, the liquidcrystalline polymer is generally considered a “high naphthenic” polymerto the extent that it contains a relatively high content of repeatingunits derived from naphthenic hydroxycarboxylic acids and naphthenicdicarboxylic acids, such as NDA, HNA, or combinations thereof. That is,the total amount of repeating units derived from naphthenichydroxycarboxylic and/or dicarboxylic acids (e.g., NDA, HNA, or acombination of HNA and NDA) is typically about 50 mol. % or more, insome embodiments about 60 mol. % or more, in some embodiments about 62mol. % or more, in some embodiments about 68 mol. % or more, in someembodiments about 70 mol. % or more, and in some embodiments, from about70 mol. % to about 80 mol. % of the polymer. Contrary to manyconventional “low naphthenic” polymers, it is believed that theresulting “high naphthenic” polymers are capable of exhibiting goodthermal and mechanical properties. Without intending to be limited bytheory, it is believed that such “high naphthenic” polymers are capableof reducing the tendency of the polymer composition to absorb water,which can help stabilize the dielectric constant and dissipation factorat high frequency ranges. Namely, such high naphthenic polymerstypically have a water adsorption of about 0.015% or less, in someembodiments about 0.01% or less, and in some embodiments, from about0.0001% to about 0.008% after being immersed in water for 24 hours inaccordance with ISO 62-1:2008. The high naphthenic polymers may alsohave a moisture adsorption of about 0.01% or less, in some embodimentsabout 0.008% or less, and in some embodiments, from about 0.0001% toabout 0.006% after being exposed to a humid atmosphere (50% relativehumidity) at a temperature of 23° C. in accordance with ISO 62-4:2008.

In one embodiment, for instance, the repeating units derived from HNAmay constitute about 50 mol. % or more, in some embodiments about 60mol. % or more, in some embodiments about 62 mol. % or more, in someembodiments about 68 mol. % or more, in some embodiments about 70 mol. %or more, and in some embodiments, from about 70 mol. % to about 80 mol.% of the polymer. The liquid crystalline polymer may also containvarious other monomers. For example, the polymer may contain repeatingunits derived from HBA in an amount of from about 10 mol. % to about 40mol. %, and in some embodiments from about 15 mol. % to about 35 mol. %,and in some embodiments, from about 20 mol. % to about 30 mol. %. Whenemployed, the molar ratio of HNA to HBA may be selectively controlledwithin a specific range to help achieve the desired properties, such asfrom about 0.1 to about 40, in some embodiments from about 0.5 to about20, in some embodiments from about 0.8 to about 10, and in someembodiments, from about 1 to about 5.

Yet other repeating units, such as aromatic dicarboxylic acids (TA, IA,etc.), aromatic diols (e.g., BP, HQ, etc.), etc., may also be employedas noted above. Nevertheless, in certain embodiments, it may be desiredto minimize the presence of such monomers in the polymer to help achievethe desired properties. For example, the total amount of aromaticdicarboxylic acid(s) (e.g., IA and/or TA) may be about 20 mol% or less,in some embodiments about 15 mol. % or less, in some embodiments about10 mol. % or less, in some embodiments, from 0 mol. % to about 5 mol. %,and in some embodiments, from 0 mol. % to about 2 mol. % of the polymer.Similarly, the total amount of aromatic dicarboxylic acid(s) (e.g., IAand/or TA) may be about 20 mol% or less, in some embodiments about 15mol. % or less, in some embodiments about 10 mol. % or less, in someembodiments, from 0 mol. % to about 5 mol. %, and in some embodiments,from 0 mol. % to about 2 mol. % of the polymer (e.g., 0 mol. %).

Regardless of the particular constituents and nature of the polymer, theliquid crystalline polymer may be prepared by initially introducing thearomatic monomer(s) used to form the ester repeating units (e.g.,aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, etc.)and/or other repeating units (e.g., aromatic diol) into a reactor vesselto initiate a polycondensation reaction. The particular conditions andsteps employed in such reactions are well known, and may be described inmore detail in U.S. Pat. No. 4,161,470 to Calundann; U.S. Pat. No.5,616,680 to Linstid, III, et al.; U.S. Pat. No. 6,114,492 to Linstid,Ill, et al.; U.S. Pat. No. 6,514,611 to Shepherd, et al.; and WO2004/058851 to Waggoner. The vessel employed for the reaction is notespecially limited, although it is typically desired to employ one thatis commonly used in reactions of high viscosity fluids. Examples of sucha reaction vessel may include a stirring tank-type apparatus that has anagitator with a variably-shaped stirring blade, such as an anchor type,multistage type, spiral-ribbon type, screw shaft type, etc., or amodified shape thereof. Further examples of such a reaction vessel mayinclude a mixing apparatus commonly used in resin kneading, such as akneader, a roll mill, a Banbury mixer, etc.

If desired, the reaction may proceed through the acetylation of themonomers as known the art. This may be accomplished by adding anacetylating agent (e.g., acetic anhydride) to the monomers. Acetylationis generally initiated at temperatures of about 90° C. During theinitial stage of the acetylation, reflux may be employed to maintainvapor phase temperature below the point at which acetic acid byproductand anhydride begin to distill. Temperatures during acetylationtypically range from between 90° C. to 150° C., and in some embodiments,from about 110° C. to about 150° C. If reflux is used, the vapor phasetemperature typically exceeds the boiling point of acetic acid, butremains low enough to retain residual acetic anhydride. For example,acetic anhydride vaporizes at temperatures of about 140° C. Thus,providing the reactor with a vapor phase reflux at a temperature of fromabout 110° C. to about 130° C. is particularly desirable. To ensuresubstantially complete reaction, an excess amount of acetic anhydridemay be employed. The amount of excess anhydride will vary depending uponthe particular acetylation conditions employed, including the presenceor absence of reflux. The use of an excess of from about 1 to about 10mole percent of acetic anhydride, based on the total moles of reactanthydroxyl groups present is not uncommon.

Acetylation may occur in in a separate reactor vessel, or it may occurin situ within the polymerization reactor vessel. When separate reactorvessels are employed, one or more of the monomers may be introduced tothe acetylation reactor and subsequently transferred to thepolymerization reactor. Likewise, one or more of the monomers may alsobe directly introduced to the reactor vessel without undergoingpre-acetylation.

In addition to the monomers and optional acetylating agents, othercomponents may also be included within the reaction mixture to helpfacilitate polymerization. For instance, a catalyst may be optionallyemployed, such as metal salt catalysts (e.g., magnesium acetate, tin(I)acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassiumacetate, etc.) and organic compound catalysts (e.g., N-methylimidazole).Such catalysts are typically used in amounts of from about 50 to about500 parts per million based on the total weight of the recurring unitprecursors. When separate reactors are employed, it is typically desiredto apply the catalyst to the acetylation reactor rather than thepolymerization reactor, although this is by no means a requirement.

The reaction mixture is generally heated to an elevated temperaturewithin the polymerization reactor vessel to initiate meltpolycondensation of the reactants. Polycondensation may occur, forinstance, within a temperature range of from about 200° C. to about 400°C., in some embodiments from about 250° C. to about 380° C., in someembodiments from about 280° C. to about 350° C., and in some embodimentsfrom about 300° C. to about 340° C. For instance, one suitable techniquefor forming the aromatic polyester may include charging precursormonomers and acetic anhydride into the reactor, heating the mixture to atemperature of from about 90° C. to about 150° C. to acetylize ahydroxyl group of the monomers (e.g., forming acetoxy), and thenincreasing the temperature to from about 280° C. to about 380° C. tocarry out melt polycondensation. As the final polymerizationtemperatures are approached, volatile byproducts of the reaction (e.g.,acetic acid) may also be removed so that the desired molecular weightmay be readily achieved. The reaction mixture is generally subjected toagitation during polymerization to ensure good heat and mass transfer,and in turn, good material homogeneity. The rotational velocity of theagitator may vary during the course of the reaction, but typicallyranges from about 10 to about 100 revolutions per minute (“rpm”), and insome embodiments, from about 20 to about 80 rpm. To build molecularweight in the melt, the polymerization reaction may also be conductedunder vacuum, the application of which facilitates the removal ofvolatiles formed during the final stages of polycondensation. The vacuummay be created by the application of a suctional pressure, such aswithin the range of from about 5 to about 30 pounds per square inch(“psi”), and in some embodiments, from about 10 to about 20 psi.

Following melt polymerization, the molten polymer may be discharged fromthe reactor, typically through an extrusion orifice fitted with a die ofdesired configuration, cooled, and collected. Commonly, the melt isdischarged through a perforated die to form strands that are taken up ina water bath, pelletized and dried. In some embodiments, the meltpolymerized polymer may also be subjected to a subsequent solid-statepolymerization method to further increase its molecular weight.Solid-state polymerization may be conducted in the presence of a gas(e.g., air, inert gas, etc.). Suitable inert gases may include, forinstance, include nitrogen, helium, argon, neon, krypton, xenon, etc.,as well as combinations thereof. The solid-state polymerization reactorvessel can be of virtually any design that will allow the polymer to bemaintained at the desired solid-state polymerization temperature for thedesired residence time. Examples of such vessels can be those that havea fixed bed, static bed, moving bed, fluidized bed, etc. The temperatureat which solid-state polymerization is performed may vary, but istypically within a range of from about 200° C. to about 400° C., in someembodiments from about 250° C. to about 380° C., in some embodimentsfrom about 280° C. to about 350° C., and in some embodiments from about300° C. to about 340° C. The polymerization time will of course varybased on the temperature and target molecular weight. In most cases,however, the solid-state polymerization time will be from about 2 toabout 12 hours, and in some embodiments, from about 4 to about 10 hours.

B. Optional Additives

Liquid crystalline polymer(s) may be employed in neat form within apolymer composition (i.e., 100 wt. % of the polymer composition), or awide variety of other additives may optionally be included within thecomposition. When employed, such additives typically constitute fromabout 1 wt. % to about 60 wt. %, in some embodiments from about 2 wt. %to about 50 wt. %, and in some embodiments, from about 5 wt. % to about40 wt. % of the polymer composition. In such embodiments, liquidcrystalline polymers may likewise constitute from about 40 wt. % toabout 99 wt. %, in some embodiments from about 50 wt. % to about 98 wt.%, and in some embodiments, from about 60 wt. % to about 95 wt. % of thepolymer composition.

A wide variety of additional additives can also be included in thepolymer composition, such as hydrophobic materials, lubricants, fibrousfillers, particulate fillers, hollow fillers, laser activatableadditives, thermally conductive fillers, pigments, antioxidants,stabilizers, surfactants, waxes, flame retardants, anti-drip additives,nucleating agents (e.g., boron nitride), flow modifiers, couplingagents, antimicrobials, pigments or other colorants, impact modifiers,and other materials added to enhance properties and processability.

In one embodiment, for instance, a hydrophobic material may be employedthat is distributed throughout the polymer matrix. Without intending tobe limited by theory, it is believed that the hydrophobic material canhelp reduce the tendency of the polymer composition to absorb water,which can help stabilize the dielectric constant and dissipation factorat high frequency ranges. Particularly suitable hydrophobic materialsare low surface energy elastomers, such as fluoropolymers, siliconepolymers, etc. Fluoropolymers, for instance, may contains a hydrocarbonbackbone polymer in which some or all of the hydrogen atoms aresubstituted with fluorine atoms. The backbone polymer may polyolefinicand formed from fluorine-substituted, unsaturated olefin monomers. Thefluoropolymer can be a homopolymer of such fluorine-substituted monomersor a copolymer of fluorine-substituted monomers or mixtures offluorine-substituted monomers and non-fluorine-substituted monomers.Along with fluorine atoms, the fluoropolymer can also be substitutedwith other halogen atoms, such as chlorine and bromine atoms.Representative monomers suitable for forming fluoropolymers for use inthis invention are tetrafluoroethylene (“TFE”), vinylidene fluoride(“VF2”), hexafluoropropylene (“HFP”), chlorotrifluoroethylene (“CTFE”),perfluoroethylvinyl ether (“PEVE”), perfluoromethylvinyl ether (“PMVE”),perfluoropropylvinyl ether (“PPVE”), etc., as well as mixtures thereof.Specific examples of suitable fluoropolymers includepolytetrafluoroethylene (“PTFE”), perfluoroalkylvinyl ether (“PVE”),poly(tetrafluoroethylene-co-perfluoroalkyvinyl ether) (“PFA”),fluorinated ethylene-propylene copolymer (“FEP”),ethylene-tetrafluoroethylene copolymer (“ETFE”), polyvinylidene fluoride(“PVDF”), polychlorotrifluoroethylene (“PCTFE”), and TFE copolymers withVF2 and/or HFP, etc., as well as mixtures thereof.

In certain embodiments, the hydrophobic material (e.g., fluoropolymer)may have a particle size that is selectively controlled to help formfilms of a relatively low thickness. For example, the hydrophobicmaterial may have a median particle size (e.g., diameter) of about 1 toabout 60 micrometers, in some embodiments from about 2 to about 55micrometers, in some embodiments from about 3 to about 50 micrometers,and in some embodiments, from about 25 to about 50 micrometers, such asdetermined using laser diffraction techniques in accordance with ISO13320:2009 (e.g., with a Horiba LA-960 particle size distributionanalyzer). The hydrophobic material may also have a narrow sizedistribution. That is, at least about 70% by volume of the particles, insome embodiments at least about 80% by volume of the particles, and insome embodiments, at least about 90% by volume of the particles may havea size within the ranges noted above.

A fibrous filler may also be employed in the polymer composition. Thefibrous filler typically includes fibers having a high degree of tensilestrength relative to their mass. For example, the ultimate tensilestrength of the fibers (determined in accordance with ASTM D2101) istypically from about 1,000 to about 15,000 Megapascals (“MPa”), in someembodiments from about 2,000 MPa to about 10,000 MPa, and in someembodiments from about 3,000 MPa to about 6,000 MPa. To help maintainthe desired dielectric properties, such high strength fibers may beformed from materials that are generally insulative in nature, such asglass, ceramics or minerals (e.g., alumina or silica), aramids (e.g.,Kevler® marketed by E. I. duPont de Nemours, Wilmington, Del.),minerals, polyolefins, polyesters, etc. The fibrous filler may includeglass fibers, mineral fibers, or a mixture thereof. For instance, in oneembodiment, the fibrous filler may include glass fibers. The glassfibers particularly suitable may include E-glass, A-glass, C-glass,D-glass, AR-glass, R-glass, S1-glass, S2-glass, etc. In anotherembodiment, the fibrous filler may include mineral fibers. The mineralfibers may include those derived from silicates, such as neosilicates,sorosilicates, inosilicates (e.g., calcium inosilicates, such aswollastonite; calcium magnesium inosilicates, such as tremolite; calciummagnesium iron inosilicates, such as actinolite; magnesium ironinosilicates, such as anthophyllite; etc.), phyllosilicates (e.g.,aluminum phyllosilicates, such as palygorskite), tectosilicates, etc.;sulfates, such as calcium sulfates (e.g., dehydrated or anhydrousgypsum); mineral wools (e.g., rock or slag wool); and so forth.Particularly suitable are inosilicates, such as wollastonite fibersavailable from Nyco Minerals under the trade designation NYGLOS® (e.g.,NYGLOS® 4W or NYGLOS® 8).

Further, although the fibrous fillers may have a variety of differentsizes, fibers having a certain aspect ratio can help improve themechanical properties of the polymer composition. That is, fibrousfillers having an aspect ratio (average length divided by nominaldiameter) of about 2 or more, in some embodiments about 4 or more, insome embodiments from about 5 to about 50, and in some embodiments fromabout 8 to about 40 may be particularly beneficial. Such fibrous fillersmay, for instance, have a weight average length of about 10 micrometeror more, in some embodiments about 25 micrometers or more, in someembodiments from about 50 micrometers or more to about 800 micrometersor less, and in some embodiments from about 60 micrometers to about 500micrometers. Also, such fibrous fillers may, for instance, have a volumeaverage length of about 10 micrometer or more, in some embodiments about25 micrometers or more, in some embodiments from about 50 micrometers ormore to about 800 micrometers or less, and in some embodiments fromabout 60 micrometers to about 500 micrometers. The fibrous fillers maylikewise have a nominal diameter of about 5 micrometers or more, in someembodiments about 6 micrometers or more, in some embodiments from about8 micrometers to about 40 micrometers, and in some embodiments fromabout 9 micrometers to about 20 micrometers. The relative amount of thefibrous filler may also be selectively controlled to help achieve thedesired mechanical and thermal properties without adversely impactingother properties of the polymer composition, such as its flowability anddielectric properties, etc. In this regard, the fibrous fillers may havea dielectric constant of about 6 or less, in some embodiments about 5.5or less, in some embodiments from about 1.1 to about 5, and in someembodiments from about 2 to about 4.8 at a frequency of 1 GHz.

The fibrous filler may be in a modified or an unmodified form, e.g.,provided with a sizing, or chemically treated, in order to improveadhesion to the plastic. In some examples, glass fibers may be providedwith a sizing to protect the glass fiber, to smooth the fiber but alsoto improve the adhesion between the fiber and a matrix material. Ifpresent, a sizing may comprise silanes, film forming agents, lubricants,wetting agents, adhesive agents optionally antistatic agents andplasticizers, emulsifiers and optionally further additives. In oneparticular embodiment, the sizing may include a silane. Specificexamples of silanes are aminosilanes, e.g. 3-trimethoxysilylpropylamine,N-(2-aminoethyl)-3-aminopropyltrimethoxy-silane,N-(3-trimethoxysilanylpropyl)ethane-1,2-diamine,3-(2-aminoethyl-amino)propyltrimethoxysilane,N-[3-(trimethoxysilyl)propyl]-1,2-ethane-diamine.

In certain other embodiments, the polymer composition may be “laseractivatable” in the sense that it contains an additive that can beactivated by a laser direct structuring (“LDS”) process. In such aprocess, the additive is exposed to a laser that causes the release ofmetals. The laser thus draws the pattern of conductive elements onto thepart and leaves behind a roughened surface containing embedded metalparticles. These particles act as nuclei for the crystal growth during asubsequent plating process (e.g., copper plating, gold plating, nickelplating, silver plating, zinc plating, tin plating, etc.). The laseractivatable additive generally includes spinel crystals, which mayinclude two or more metal oxide cluster configurations within adefinable crystal formation. For example, the overall crystal formationmay have the following general formula:

AB₂O₄

wherein,

A is a metal cation having a valance of 2, such as cadmium, chromium,manganese, nickel, zinc, copper, cobalt, iron, magnesium, tin, titanium,etc., as well as combinations thereof; and

B is a metal cation having a valance of 3, such as chromium, iron,aluminum, nickel, manganese, tin, etc., as well as combinations thereof.

Typically, A in the formula above provides the primary cation componentof a first metal oxide cluster and B provides the primary cationcomponent of a second metal oxide cluster. These oxide clusters may havethe same or different structures. In one embodiment, for example, thefirst metal oxide cluster has a tetrahedral structure and the secondmetal oxide cluster has an octahedral cluster. Regardless, the clustersmay together provide a singular identifiable crystal type structurehaving heightened susceptibility to electromagnetic radiation. Examplesof suitable spinel crystals include, for instance, MgAl₂O₄, ZnAl₂O₄,FeAl₂O₄, CuFe₂O₄, CuCr₂O₄, MnFe₂O₄, NiFe₂O₄, TiFe₂O₄, FeCr₂O₄, MgCr₂O₄,etc. Copper chromium oxide (CuCr₂O₄) is particularly suitable for use inthe present invention and is available from Shepherd Color Co. under thedesignation “Shepherd Black 1GM.

The polymer composition may also include one or more hollow inorganicfillers to help achieve the desired dielectric constant. For instance,such fillers may have a dielectric constant of about 3.0 or less, insome embodiments about 2.5 or less, in some embodiments from about 1.1to about 2.3, and in some embodiments from about 1.2 to about 2.0 at 100MHz. The hollow inorganic fillers typically have an interior hollowspace or cavity and may be synthesized using techniques known in theart. The hollow inorganic fillers may be made from conventionalmaterials. For instance, the hollow inorganic fillers may includealumina, silica, zirconia, magnesia, glass, fly ash, borate, phosphate,ceramic, and the like. In one embodiment, the hollow inorganic fillersmay include hollow glass fillers, hollow ceramic fillers, and mixturesthereof. In one embodiment, the hollow inorganic fillers include hollowglass fillers. The hollow glass fillers may be made from a soda limeborosilicate glass, a soda lime glass, a borosilicate glass, a sodiumborosilicate glass, a sodium silicate glass, or an aluminosilicateglass. In this regard, in one embodiment, the composition of the glass,while not limited, may be at least about 65% by weight of SiO₂, 3-15% byweight of Na₂O, 8-15% by weight of CaO, 0.1-5% by weight of MgO, 0.01-3%by weight of Al₂O₃, 0.01-1% by weight of K₂O, and optionally otheroxides (e.g., Li₂O, Fe₂O₃, TiO₂, B₂O₃). In another embodiment, thecomposition may be about 50-58% by weight of SiO₂, 25-30% by weight ofAl₂O₃, 6-10% by weight of CaO, 1-4% by weight of Na₂O/K₂O, and 1-5% byweight of other oxides. Also, in one embodiment, the hollow glassfillers may include more alkaline earth metal oxides than alkali metaloxides. For example, the weight ratio of the alkaline earth metal oxidesto the alkali metal oxides may be more than 1, in some embodiments about1.1 or more, in some embodiments about 1.2 to about 4, and in someembodiments from about 1.5 to about 3. Regardless of the above, itshould be understood that the glass composition may vary depending onthe type of glass utilized and still provide the benefits as desired bythe present invention.

The hollow inorganic fillers may have at least one dimension having anaverage value that is about 1 micrometers or more, in some embodimentsabout 5 micrometers or more, in some embodiments about 8 micrometers ormore, in some embodiments from about 1 micrometer to about 150micrometers, in some embodiments from about 10 micrometers to about 150micrometers, and in some embodiments from about 12 micrometers to about50 micrometers. In one embodiment, such average value may refer to a d50value. Furthermore, the hollow inorganic fillers may have a D₁₀ of about3 micrometers or more, in some embodiments about 4 micrometers or more,in some embodiments from about 5 micrometers to about 20 micrometers,and in some embodiments from about 6 micrometers to about 15micrometers. The hollow inorganic fillers may have a D₉₀ of about 10micrometers or more, in some embodiments about 15 micrometers or more,in some embodiments from about 20 micrometers to about 150 micrometers,and in some embodiments from about 22 micrometers to about 50micrometers. In this regard, the hollow inorganic fillers may be presentin a size distribution, which may be a Gaussian, normal, or non-normalsize distribution. In one embodiment, the hollow inorganic fillers mayhave a Gaussian size distribution. In another embodiment, the hollowinorganic fillers may have a normal size distribution. In a furtherembodiment, the hollow inorganic fillers may have a non-normal sizedistribution. Examples of non-normal size distributions may includeunimodal and multi-modal (e.g., bimodal) size distributions. Whenreferring to dimensions above, such dimension may be any dimension. Inone embodiment, however, such dimension refers to a diameter. Forexample, such value for the dimension refers to an average diameter ofspheres. The dimension, such as the average diameter, may be determinedin accordance to 3M QCM 193.0. In this regard, in one embodiment, thehollow inorganic fillers may be referring to hollow spheres such ashollow glass spheres. For instance, the hollow inorganic fillers mayhave an average aspect ratio of approximately 1. In general, the averageaspect ratio may be about 0.8 or more, in some embodiments about 0.85 ormore, in some embodiments from about 0.9 to about 1.3, and in someembodiments from about 0.95 to about 1.05.

In addition, the hollow inorganic fillers may have relatively thin wallsto help with the dielectric properties of the polymer composition aswell as the reduction in weight. The thickness of the wall may be about50% or less, in some embodiments about 40% or less, in some embodimentsfrom about 1% to about 30%, and in some embodiments from about 2% toabout 25% the average dimension, such as the average diameter, of thehollow inorganic fillers. In addition, the hollow inorganic fillers mayhave a certain true density that can allow for easy handling and providea polymer composition having a reduction in weight. In general, the truedensity refers to the quotient obtained by dividing the mass of a sampleof the hollow fillers by the true volume of that mass of hollow fillerswherein the true volume is referred to as the aggregate total volume ofthe hollow fillers. In this regard, the true density of the hollowinorganic fillers may be about 0.1 g/cm³ or more, in some embodimentsabout 0.2 g/cm³ or more, in some embodiments from about 0.3 g/cm³ ormore to about 1.2 g/cm³, and in some embodiments from about 0.4 g/cm³ ormore to about 0.9 g/cm³. The true density may be determined inaccordance to 3M QCM 14.24.1.

Even though the fillers are hollow, they may have a mechanical strengththat allows for maintaining the integrity of the structure of thefillers resulting in a lower likelihood of the fillers being brokenduring processing and/or use. In this regard, the isotactic crushresistance (i.e., wherein at least 80 vol. %, such as at least 90 vol. %of the hollow fillers survive) of the hollow inorganic fillers may beabout 20 MPa or more, in some embodiments about 100 MPa or more, in someembodiments from about 150 MPa to about 500 MPa, and in some embodimentsfrom about 200 MPa to about 350 MPa. The isotactic crush resistance maybe determined in accordance to 3M QCM 14.1.8.

The alkalinity of the hollow inorganic fillers may be about 1.0 meq/g orless, in some embodiments about 0.9 meq/g or less, in some embodimentsfrom about 0.1 meq/g to about 0.8 meq/g, and in some embodiments fromabout 0.2 meq/g to about 0.7 meq/g. The alkalinity may be determined inaccordance to 3M QCM 55.19. In order to provide a relatively lowalkalinity, the hollow inorganic fillers may be treated with a suitableacid, such as a phosphoric acid. In addition, the hollow inorganicfillers may also include a surface treatment to assist with providing abetter compatibility with the polymer and/or other components within thepolymer composition. As an example, the surface treatment may be asilanization. In particular, the surface treatment agents may include,but are not limited to, aminosilanes, epoxysilanes, etc.

If desired, a particulate filler may be employed for improving certainproperties of the polymer composition. In certain embodiments, particlesmay be employed that have a certain hardness value to help improve thesurface properties of the composition. For instance, the hardness valuesmay be about 2 or more, in some embodiments about 2.5 or more, in someembodiments from about 3 to about 11, in some embodiments from about 3.5to about 11, and in some embodiments, from about 4.5 to about 6.5 basedon the Mohs hardness scale. Examples of such particles may include, forinstance, silica (Mohs hardness of 7), mica (e.g., Mohs hardness ofabout 3); carbonates, such as calcium carbonate (CaCO₃, Mohs hardness of3.0) or a copper carbonate hydroxide (Cu₂CO₃(OH)₂, Mohs hardness of4.0); fluorides, such as calcium fluoride (CaFl₂, Mohs hardness of 4.0);phosphates, such as calcium pyrophosphate ((Ca₂P₂O₇, Mohs hardness of5.0), anhydrous dicalcium phosphate (CaHPO₄, Mohs hardness of 3.5), orhydrated aluminum phosphate (AlPO₄.2H₂O, Mohs hardness of 4.5); borates,such as calcium borosilicate hydroxide (Ca₂B₅SiO₉(OH)5, Mohs hardness of3.5); alumina (AlO₂, Mohs hardness of 10.0); sulfates, such as calciumsulfate (CaSO₄, Mohs hardness of 3.5) or barium sulfate (BaSO₄, Mohshardness of from 3 to 3.5); and so forth, as well as combinationsthereof.

The shape of the particles may vary as desired. For instance,flake-shaped particles may be employed in certain embodiments that havea relatively high aspect ratio (e.g., average diameter divided byaverage thickness), such as about 10:1 or more, in some embodimentsabout 20:1 or more, and in some embodiments, from about 40:1 to about200:1. The average diameter of the particles may, for example, rangefrom about 5 micrometers to about 200 micrometers, in some embodimentsfrom about 30 micrometers to about 150 micrometers, and in someembodiments, from about 50 micrometers to about 120 micrometers, such asdetermined using laser diffraction techniques in accordance with ISO13320:2009 (e.g., with a Horiba LA-960 particle size distributionanalyzer). Suitable flaked-shaped particles may be formed from a naturaland/or synthetic silicate mineral, such as mica, halloysite, kaolinite,illite, montmorillonite, vermiculite, palygorskite, pyrophyllite,calcium silicate, aluminum silicate, wollastonite, etc. Mica, forinstance, is particularly suitable. Any form of mica may generally beemployed, including, for instance, muscovite (KAl₂(AlSi₃)O₁₀(OH)₂),biotite (K(Mg,Fe)₃(AlSi₃)O₁₀(OH)₂), phlogopite (KMg₃(AlSi₃)O₁₀(OH)₂),lepidolite (K(Li,Al)₂₋₃(AlSi₃)O₁₀(OH)₂), glauconite(K,Na)(Al,Mg,Fe)₂(Si,Al)₄O₁₀(OH)₂), etc. Granular particles may also beemployed. Typically, such particles have an average diameter of fromabout 0.1 to about 10 micrometers, in some embodiments from about 0.2 toabout 4 micrometers, and in some embodiments, from about 0.5 to about 2micrometers, such as determined using laser diffraction techniques inaccordance with ISO 13320:2009 (e.g., with a Horiba LA-960 particle sizedistribution analyzer). Particularly suitable granular fillers mayinclude, for instance, talc, barium sulfate, calcium sulfate, calciumcarbonate, etc.

The particulate filler may be formed primarily or entirely from one typeof particle, such as flake-shaped particles (e.g., mica) or granularparticles (e.g., barium sulfate). That is, such flaked-shaped orgranular particles may constitute about 50 wt. % or more, and in someembodiments, about 75 wt. % or more (e.g., 100 wt. %) of the particulatefiller. Of course, in other embodiments, flake-shaped and granularparticles may also be employed in combination. In such embodiments, forexample, flake-shaped particles may constitute from about 0.5 wt. % toabout 20 wt. %, and in some embodiments, from about 1 wt. % to about 10wt. % of the particulate filler, while the granular particles constitutefrom about 80 wt. % to about 99.5 wt. %, and in some embodiments, fromabout 90 wt. % to about 99 wt. % of the particulate filler.

If desired, the particles may also be coated with a fluorinated additiveto help improve the processing of the composition, such as by providingbetter mold filling, internal lubrication, mold release, etc. Thefluorinated additive may include a fluoropolymer, which contains ahydrocarbon backbone polymer in which some or all of the hydrogen atomsare substituted with fluorine atoms. The backbone polymer maypolyolefinic and formed from fluorine-substituted, unsaturated olefinmonomers. The fluoropolymer can be a homopolymer of suchfluorine-substituted monomers or a copolymer of fluorine-substitutedmonomers or mixtures of fluorine-substituted monomers andnon-fluorine-substituted monomers. Along with fluorine atoms, thefluoropolymer can also be substituted with other halogen atoms, such aschlorine and bromine atoms. Representative monomers suitable for formingfluoropolymers for use in this invention are tetrafluoroethylene,vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene,perfluoroethylvinyl ether, perfluoromethylvinyl ether,perfluoropropylvinyl ether, etc., as well as mixtures thereof. Specificexamples of suitable fluoropolymers include polytetrafluoroethylene,perfluoroalkylvinyl ether,poly(tetrafluoroethylene-co-perfluoroalkyvinylether), fluorinatedethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer,polyvinylidene fluoride, polychlorotrifluoroethylene, etc., as well asmixtures thereof.

II. Formation

The components used to form the polymer composition may be combinedtogether using any of a variety of different techniques as is known inthe art. In one particular embodiment, for example, the liquidcrystalline polymer and other optional additives are melt processed as amixture within an extruder to form the polymer composition. Thecomponents may be melt-kneaded in a single-screw or multi-screw extruderat a temperature of from about 200° C. to about 450° C. In oneembodiment, the mixture may be melt processed in an extruder thatincludes multiple temperature zones. The temperature of individual zonesis typically set within about −60° C. to about 25° C. relative to themelting temperature of the polymer. By way of example, the mixture maybe melt processed using a twin screw extruder such as a Leistritz 18-mmco-rotating fully intermeshing twin screw extruder. A general purposescrew design can be used to melt process the mixture. In one embodiment,the mixture including all of the components may be fed to the feedthroat in the first barrel by means of a volumetric feeder. In anotherembodiment, different components may be added at different additionpoints in the extruder, as is known. For example, the polymer may beapplied at the feed throat, and optional additives may be supplied atthe same or different temperature zone located downstream therefrom.Regardless, the resulting composition can be melted and mixed thenextruded through a die. The extruded polymer composition can then bequenched in a water bath to solidify and granulated in a pelletizerfollowed by drying.

Regardless of the manner in which the composition is formed, theresulting melt viscosity is generally low enough that it can readilyform a melt-extruded substrate. For example, in one particularembodiment, the polymer composition may have a melt viscosity of about500 Pa-s or less, in some embodiments about 250 Pa-s or less, in someembodiments from about 5 Pa-s to about 150 Pa-s, in some embodimentsfrom about 5 Pa-s to about 100 Pa-s, in some embodiments from about 10Pa-s to about 100 Pa-s, in some embodiments from about 15 to about 90Pa-s, as determined at a shear rate of 1,000 seconds⁻¹.

II. Film

As noted above, the liquid crystalline polymer composition of thepresent invention is particularly well suited for use in films. Any ofvariety of different techniques may generally be used to form thepolymer composition into a film. Suitable film-forming techniques mayinclude, for instance, flat sheet die extrusion, blown film extrusion,tubular trapped bubble film processes, etc. In one particularembodiment, a flat sheet die extrusion process is employed that utilizesa T-shaped die. The die typically contains arms that extend at rightangles from an initial extrusion channel. The arms may have a slit alongtheir length to allow the polymer melt to flow therethrough. Examples ofsuch film extrusion processes are described, for instance, in U.S. Pat.No. 4,708,629 to Kasamatsu. In another embodiment, a blown film processmay be employed in which the composition is fed to an extruder, where itis melt processed and then supplied through a blown film die to form amolten bubble. Typically, the die contains a mandrel that is positionedwithin the interior of an outer die body so that a space is definedtherebetween. The polymer composition is blown through this space toform the bubble, which can then be drawn, inflated with air, and rapidlycooled so that the polymer composition quickly solidifies. If desired,the bubble may then be collapsed between rollers and optionally woundonto a reel.

In one particular embodiment, a film may be formed from the polymercomposition that has a thickness of from about 0.5 to about 500micrometers, in some embodiments from about 1 to about 250 micrometers,in some embodiments from about 2 to about 150 micrometers, in someembodiments from about 3 to about 100 micrometers, and in someembodiments, from about 5 to about 60 micrometers. Likewise, thick films(or sheets) may have a thickness of from about 500 micrometers to about25 millimeters, in some embodiments from about 600 micrometers to about20 millimeters, and in some embodiments, from about 1 millimeter toabout 10 millimeters.

Due to the unique properties of the liquid crystalline polymercomposition, a film may be formed therefrom that exhibits goodmechanical properties. One parameter that is indicative of the relativestrength of the film is the tensile strength, which is equal to the peakstress obtained in a stress-strain curve. Desirably, the film exhibits atensile strength in the machine direction (“MD”) of from about 100 toabout 800 Megapascals (MPa), in some embodiments from about 150 to about600 MPa, and in some embodiments, from about 200 to about 400 MPa, and atensile strength in the transverse direction (“TD”) of from about 1 toabout 50 Megapascals (MPa), in some embodiments from about 5 to about 40MPa, and in some embodiments, from about 10 to about 30 MPa. The filmmay also be ductile and thus exhibit a high elongation at break in theMD and/or TD, such as about 2% or more, in some embodiments about 5% ormore, in some embodiments from about 15% to about 50%, and in someembodiments, from about 15% to about 40%. Although possessing goodstrength and ductility, the film is not too stiff. One parameter that isindicative of the relative stiffness of the film is Young's modulus. Forexample, the film typically exhibits a Young's modulus in the MD of fromabout 10,000 to about 80,000 MPa, in some embodiments from about 12,000to about 50,000 MPa, and in some embodiments, from about 15,000 to about30,000 MPa, and a Young's modulus in the TD of from about 300 to about10,000 MPa, in some embodiments from about 500 to about 5,000 MPa, andin some embodiments, from about 800 to about 3,000 MPa. The tensileproperties described above may, for example, be determined in accordancewith ASTM ISO 527-3:2018.

The resulting film may be used as a stand-alone product or incorporatedinto other types of products. For example, the film can be used in astand-alone form as a shrink film, cling film, stretch film, sealingfilm, etc., or to form a package for food products (e.g., snackpackaging, heavy duty bags, grocery sacks, baked and frozen foodpackaging, etc.), packaging for medical products, packaging forbiological materials, packaging for electronic devices, thermoformedarticles, etc.

The film can also be formed into a laminate material having a variety ofdifferent uses, such as in claddings, multi-layer print wiring boardsfor semiconductor package and mother boards, flexible printed circuitboard, tape automated bonding, tag tape, for electromagnetic waves,probe cables, communication equipment circuits, etc. In one particularembodiment, a laminate is employed in a flexible printed circuit boardthat contains at least one conductive layer and a film formed asdescribed herein. The film may be positioned adjacent to at leastconductive layer to form the laminate. The conductive layer may beprovided in a variety of different forms, such as membranes, films,molds, wafers, tubes, etc. For example, the layer may have a foil-likestructure in that it is relatively thin, such as having a thickness ofabout 500 micrometers or less, in some embodiments about 200 micrometersor less, and in some embodiments, from about 1 to about 100 micrometers.Of course, higher thicknesses may also be employed. The conductive layermay also contain a variety of conductive materials, such as a metal,e.g. gold, silver, nickel, aluminum, copper, as well as mixture oralloys thereof. In one embodiment, for instance, the conductive layermay include copper (e.g., pure copper and copper alloys).

The film may be applied to the conductive layer using techniques such asdescribed above (e.g., casting), or the conductive layer mayalternatively be applied to the film using techniques such as ion beamsputtering, high frequency sputtering, direct current magnetronsputtering, glow discharge, etc. If desired, the film may be subjectedto a surface treatment on a side facing the conductive layer so that theadhesiveness between the film and conductive layer is improved. Examplesof such surface treatments include, for instance, corona dischargetreatment, UV irradiation treatment, plasma treatment, etc. When appliedto a conductive layer, the film may be optionally annealed to improveits properties. For example, annealing may occur at a temperature offrom about 250° C. to about 400° C., in some embodiments from about 260°C. to about 350° C., and in some embodiments, from about 280° C. toabout 330° C., and for a time period ranging from about 15 minutes toabout 300 minutes, in some embodiments from about 20 minutes to about200 minutes, and in some embodiments, from about 30 minutes to about 120minutes. During annealing, it is sometimes desirable to restrain thefilm at one or more locations (e.g., edges) so that it is not generallycapable of physical movement. This may be accomplished in a variety ofways, such as by clamping, taping, or otherwise adhering the film to theconductive layer. Adhesives may also be employed between the film andthe conductive layer as is known in the art. Suitable adhesives mayinclude epoxy, phenol, polyester, nitrile, acryl, polyimide,polyurethane resins, etc.

The laminate may have a two-layer structure containing only the film andconductive layer. Referring to FIG. 6, for example, one embodiment ofsuch a two layer structure 10 is shown as containing a film 11positioned adjacent to a conductive layer 12 (e.g., copper foil).Alternatively, a multi-layered laminate may be formed that contains twoor more conductive layers and/or two or more films. Referring to FIG. 7,for example, one embodiment of a three-layer laminate structure 100 isshown that contains a film 110 positioned between two conductive layers112. Yet another embodiment is shown in FIG. 8. In this embodiment, aseven-layered laminate structure 200 is shown that contains a core 201formed from a film 210 positioned between two conductive layers 212.Films 220 likewise overlie each of the conductive layers 212,respectively, and external conductive layers 222 overlie the films 220.In the embodiments described above, the film of the present inventionmay be used to form any, or even all of the film layers. Variousconventional processing steps may be employed to provide the laminatewith sufficient strength. For example, the laminate may be pressedand/or subjected to heat treatment as is known in the art.

IV. Applications

The laminate of the present invention may be employed in a wide varietyof different applications. For example, as noted above, the laminate maybe employed in a circuit board (e.g., printed circuit board) of anelectronic device that is provided with antenna elements. The antennaelements may be applied (e.g., printed) directly onto the circuit board,or alternatively they may be provided in an antenna module that issupported by and connected to the circuit board. Referring to FIG. 9,for instance, one embodiment of an electronic device 140 is shown thatcontains a substrate 154 that supports various electrical components142, such as integrated circuits (e.g., transceiver circuitry, controlcircuitry, etc.), discrete components (e.g., capacitors, inductors,resistors), switches, and so forth. An encapsulant material 156 may bebe applied over the components 142 and a printed circuit board 154, suchas described herein, that contains conductive traces 152 and contactpads 150 for forming electrical signal paths. A semiconductor die 144may also be employed that is bonded to the printed circuit board andembedded within the package body to form each respective component 142.More particularly, the components 142 may have contacts 146 (e.g.,solder pads) and may be mounted to contacts 150 on the printed circuitboard 154 using a conductive material 148 (e.g., solder) coupled betweencontacts 146 and contacts 150. In the illustrated embodiment, antennaelements 160 are formed on an exposed surface of the encapsulantmaterial 156. The antenna elements 156 may be electrically connected tothe printed circuit board 154 via a transmission line 158 (e.g. metalpost).

In certain embodiments, the printed circuit board is specificallyconfigured for use in a 5G antenna system. As used herein, “5G”generally refers to high speed data communication over radio frequencysignals. 5G networks and systems are capable of communicating data atmuch faster rates than previous generations of data communicationstandards (e.g., “4G, “LTE”). Various standards and specifications havebeen released quantifying the requirements of 5G communications. As oneexample, the International Telecommunications Union (ITU) released theInternational Mobile Telecommunications-2020 (“IMT-2020”) standard in2015. The IMT-2020 standard specifies various data transmission criteria(e.g., downlink and uplink data rate, latency, etc.) for 5G. TheIMT-2020 Standard defines uplink and downlink peak data rates as theminimum data rates for uploading and downloading data that a 5G systemmust support. The IMT-2020 standard sets the downlink peak data raterequirement as 20 Gbit/s and the uplink peak data rate as 10 Gbit/s. Asanother example, 3^(rd) Generation Partnership Project (3GPP) recentlyreleased new standards for 5G, referred to as “5G NR.” 3GPP published“Release 15” in 2018 defining “Phase 1” for standardization of 5G NR.3GPP defines 5G frequency bands generally as “Frequency Range 1” (FR1)including sub-6 GHz frequencies and “Frequency Range 2” (FR2) asfrequency bands ranging from 20-60 GHz. However, as used herein “5Gfrequencies” can refer to systems utilizing frequencies greater than 60GHz, for example ranging up to 80 GHz, up to 150 GHz, and up to 300 GHz.As used herein, “5G frequencies” can refer to frequencies that are about2.5 GHz or higher, in some embodiments about 3.0 GHz or higher, in someembodiments from about 3 GHz to about 300 GHz, or higher, in someembodiments from about 4 GHz to about 80 GHz, in some embodiments fromabout 5 GHz to about 80 GHz, in some embodiments from about 20 GHz toabout 80 GHz, and in some embodiments from about 28 GHz to about 60 GHz.

5G antenna systems generally employ high frequency antennas and antennaarrays for use in base stations, repeaters (e.g., “femtocells”), relaystations, terminals, user devices, and/or other suitable components of5G systems. The antenna elements/arrays and systems can satisfy orqualify as “5G” under standards released by 3GPP, such as Release 15(2018), and/or the IMT-2020 Standard. To achieve such high speed datacommunication at high frequencies, antenna elements and arrays generallyemploy small feature sizes/spacing (e.g., fine pitch technology) and/oradvanced materials that can improve antenna performance. For example,the feature size (spacing between antenna elements, width of antennaelements) etc. is generally dependent on the wavelength (“λ”) of thedesired transmission and/or reception radio frequency propagatingthrough the circuit board on which the antenna element is formed (e.g.,nλ/4 where n is an integer). Further, beamforming and/or beam steeringcan be employed to facilitate receiving and transmitting across multiplefrequency ranges or channels (e.g., multiple-in-multiple-out (MIMO),massive MIMO). The high frequency 5G antenna elements can have a varietyof configurations. For example, the 5G antenna elements can be orinclude co-planar waveguide elements, patch arrays (e.g., mesh-gridpatch arrays), other suitable 5G antenna configurations. The antennaelements can be configured to provide MIMO, massive MIMO functionality,beam steering, etc. As used herein “massive” MIMO functionalitygenerally refers to providing a large number transmission and receivingchannels with an antenna array, for example 8 transmission (Tx) and 8receive (Rx) channels (abbreviated as 8×8). Massive MIMO functionalitymay be provided with 8×8, 12×12, 16×16, 32×32, 64×64, or greater.

The antenna elements may be fabricated using a variety of manufacturingtechniques. As one example, the antenna elements and/or associatedelements (e.g., ground elements, feed lines, etc.) can employ fine pitchtechnology. Fine pitch technology generally refers to small or finespacing between their components or leads. For example, featuredimensions and/or spacing between antenna elements (or between anantenna element and a ground plane) can be about 1,500 micrometers orless, in some embodiments 1,250 micrometers or less, in some embodiments750 micrometers or less (e.g., center-to-center spacing of 1.5 mm orless), 650 micrometers or less, in some embodiments 550 micrometers orless, in some embodiments 450 micrometers or less, in some embodiments350 micrometers or less, in some embodiments 250 micrometers or less, insome embodiments 150 micrometers or less, in some embodiments 100micrometers or less, and in some embodiments 50 micrometers or less.However, it should be understood that feature sizes and/or spacings thatare smaller and/or larger may also be employed. As a result of suchsmall feature dimensions, antenna configurations and/or arrays can beachieved with a large number of antenna elements in a small footprint.For example, an antenna array can have an average antenna elementconcentration of greater than 1,000 antenna elements per squarecentimeter, in some embodiments greater than 2,000 antenna elements persquare centimeter, in some embodiments greater than 3,000 antennaelements per square centimeter, in some embodiments greater than 4,000antenna elements per square centimeter, in some embodiments greater than6,000 antenna elements per square centimeter, and in some embodimentsgreater than about 8,000 antenna elements per square centimeter. Suchcompact arrangement of antenna elements can provide a greater number ofchannels for MIMO functionality per unit area of the antenna area. Forexample, the number of channels can correspond with (e.g., be equal toor proportional with) the number of antenna elements.

Referring to FIG. 1, for example, a 5G antenna system 100 can include abase station 102, one or more relay stations 104, one or more usercomputing devices 106, one or more Wi-Fi repeaters 108 (e.g.,“femtocells”), and/or other suitable antenna components for the 5Gantenna system 100. The relay stations 104 can be configured tofacilitate communication with the base station 102 by the user computingdevices 106 and/or other relay stations 104 by relaying or “repeating”signals between the base station 102 and the user computing devices 106and/or relay stations 104. The base station 102 can include a MIMOantenna array 110 configured to receive and/or transmit radio frequencysignals 112 with the relay station(s) 104, Wi-Fi repeaters 108, and/ordirectly with the user computing device(s) 106. The user computingdevice 306 is not necessarily limited by the present invention andinclude devices such as 5G smartphones.

The MIMO antenna array 110 can employ beam steering to focus or directradio frequency signals 112 with respect to the relay stations 104. Forexample, the MIMO antenna array 110 can be configured to adjust anelevation angle 114 with respect to an X-Y plane and/or a heading angle116 defined in the Z-Y plane and with respect to the Z direction.Similarly, one or more of the relay stations 104, user computing devices106, Wi-Fi repeaters 108 can employ beam steering to improve receptionand/or transmission ability with respect to MIMO antenna array 110 bydirectionally tuning sensitivity and/or power transmission of the device104, 106, 108 with respect to the MIMO antenna array 110 of the basestation 102 (e.g., by adjusting one or both of a relative elevationangle and/or relative azimuth angle of the respective devices).

FIGS. 2A-2B likewise illustrate a top-down and side elevation view,respectively, of an example user computing device 106. The usercomputing device 106 may include one or more antenna elements 200, 202(e.g., arranged as respective antenna arrays). Referring to FIG. 2A, theantenna elements 200, 202 can be configured to perform beam steering inthe X-Y plane (as illustrated by arrows 204, 206 and corresponding witha relative azimuth angle). Referring to FIG. 2B, the antenna elements200, 202 can be configured to perform beam steering in the Z-Y plane (asillustrated by arrows 204, 206).

FIG. 3 depicts a simplified schematic view of a plurality of antennaarrays 302 connected using respective feed lines 304 (e.g., with a frontend module). The antenna arrays 302 can be mounted to a side surface 306of the substrate 308, such as described and illustrated with respect toFIGS. 4A through 4C. The substrate 308 may be a circuit board such asdescribed herein. The antenna arrays 302 can include a plurality ofvertically connected elements (e.g., as a mesh-grid array). Thus, theantenna array 302 can generally extend parallel with the side surface306 of the substrate 308. Shielding can optionally be provided on theside surface 306 of the substrate 308 such that the antenna arrays 302are located outside of the shielding with respect to the substrate 308.The vertical spacing distance between the vertically connected elementsof the antenna array 302 can correspond with the “feature sizes” of theantenna arrays 320. As such, in some embodiments, these spacingdistances may be relatively small (e.g., less than about 750micrometers) such that the antenna array 302 is a “fine pitch” antennaarray 302.

FIG. 4 illustrates a side elevation view of a co-planar waveguideantenna 400 configuration. One or more co-planar ground layers 402 canbe arranged parallel with an antenna element 404 (e.g., a patch antennaelement). Another ground layer 406 may be spaced apart from the antennaelement by a substrate 408, which may be a circuit board such asdescribed herein. One or more additional antenna elements 410 can bespaced apart from the antenna element 404 by a second layer or substrate412, which may be a circuit board as described herein. The dimensions“G” and “W” may correspond with “feature sizes” of the antenna 400. The“G” dimension may correspond with a distance between the antenna element404 and the co-planar ground layer(s) 406. The “W” dimension cancorrespond with a width (e.g., linewidth) of the antenna element 404. Assuch, in some embodiments, dimensions “G” and “W” may be relativelysmall (e.g., less than about 750 micrometers) such that the antenna 400is a “fine pitch” antenna 400.

FIG. 5A illustrates one embodiment of an antenna array 500. The antennaarray 500 can include a substrate 510 and a plurality of antennaelements 520 formed thereon. The substrate 510 may be a circuit boardsuch as described herein. The plurality of antenna elements 520 can beapproximately equally sized in the X- and/or Y-directions (e.g., squareor rectangular). The plurality of antenna elements 520 can be spacedapart approximately equally in the X- and/or Y-directions. Thedimensions of the antenna elements 520 and/or spacing therebetween cancorrespond with “feature sizes” of the antenna array 500. As such, insome embodiments, the dimensions and/or spacing may be relatively small(e.g., less than about 750 micrometers) such that the antenna array 500is a “fine pitch” antenna array 500. As illustrated by the ellipses 522,the number of columns of antenna elements 520 illustrated in FIG. 5 isprovided as an example only. Similarly, the number of rows of antennaelement 520 is provided as an example only.

The tuned antenna array 500 can be used to provide massive MIMOfunctionality, for example in a base station (e.g., as described abovewith respect to FIG. 1). More specifically, radio frequency interactionsbetween the various elements can be controlled or tuned to providemultiple transmitting and/or receiving channels. Transmitting powerand/or receiving sensitivity can be directionally controlled to focus ordirect radio frequency signals, for example as described with respect tothe radio frequency signals 112 of FIG. 1. The tuned antenna array 500can provide a large number of antenna elements 522 in a small footprint.For example, the tuned antenna 500 can have an average antenna elementconcentration of 1,000 antenna elements per square cm or greater. Suchcompact arrangement of antenna elements can provide a greater number ofchannels for MIMO functionality per unit area. For example, the numberof channels can correspond with (e.g., be equal to or proportional with)the number of antenna elements.

FIG. 5B illustrates an embodiment of an antenna array 540. The antennaarray 540 can include a plurality of antenna elements 542 and pluralityof feed lines 544 connecting the antenna elements 542 (e.g., with otherantenna elements 542, a front end module, or other suitable component).The antenna elements 542 can have respective widths “w” and spacingdistances “S₁” and “S₂” therebetween (e.g., in the X-direction andY-direction, respectively). These dimensions can be selected to achieve5G radio frequency communication at a desired 5G frequency. Morespecifically, the dimensions can be selected to tune the antenna array540 for transmission and/or reception of data using radio frequencysignals that are within the 5G frequency spectrum (e.g., greater the 2.5GHz and/or greater than 3 GHz and/or greater than 28 GHz). Thedimensions can be selected based on the material properties of thesubstrate, which may be the circuit board of the present invention. Forexample, one or more of “w”, “S₁,” or “S₂” can correspond with amultiple of a propagation wavelength (“λ”) of the desired frequencythrough the substrate material (e.g., nλ/4 where n is an integer).

As one example, A can be calculated as follows:

$\lambda = \frac{c}{f\sqrt{\in_{R}}}$

where c is the speed of light in a vacuum, ∈_(R) is the dielectricconstant of the substrate (or surrounding material), f is the desiredfrequency.

FIG. 5C illustrates an example antenna configuration 560 according toaspects of the present invention. The antenna configuration 560 caninclude multiple antenna elements 562 arranged in parallel long edges ofa substrate 564. The various antenna elements 562 can have respectivelengths, “L” (and spacing distances therebetween) that tune the antennaconfiguration 560 for reception and/or transmission at a desiredfrequency and/or frequency range. More specifically, such dimensions canbe selected based on a propagation wavelength, λ, at the desiredfrequency for the substrate material, for example as described abovewith reference to FIG. 5B.

The present invention may be better understood with reference to thefollowing examples.

Test Methods

Melt Viscosity: The melt viscosity (Pa-s) may be determined inaccordance with ISO Test No. 11443:2005 at a shear rate of 1,000 s⁻¹ andtemperature 15° C. above the melting temperature (e.g., about 350° C.)using a Dynisco LCR7001 capillary rheometer. The rheometer orifice (die)had a diameter of 1 mm, length of 20 mm, L/D ratio of 20.1, and anentrance angle of 180°. The diameter of the barrel was 9.55 mm +0.005 mmand the length of the rod was 233.4 mm.

Melting Temperature: The melting temperature (“Tm”) may be determined bydifferential scanning calorimetry (“DSC”) as is known in the art. Themelting temperature is the differential scanning calorimetry (DSC) peakmelt temperature as determined by ISO Test No. 11357-2:2013. Under theDSC procedure, samples were heated and cooled at 20° C. per minute asstated in ISO Standard 10350 using DSC measurements conducted on a TAQ2000 Instrument.

Deflection Temperature Under Load (“DTUL”): The deflection under loadtemperature may be determined in accordance with ISO Test No. 75-2:2013(technically equivalent to ASTM D648-07). More particularly, a teststrip sample having a length of 80 mm, thickness of 10 mm, and width of4 mm may be subjected to an edgewise three-point bending test in whichthe specified load (maximum outer fibers stress) was 1.8 Megapascals.The specimen may be lowered into a silicone oil bath where thetemperature is raised at 2° C. per minute until it deflects 0.25 mm(0.32 mm for ISO Test No. 75-2:2013).

Tensile Modulus, Tensile Stress, and Tensile Elongation: Tensileproperties may be tested according to ISO Test No. 527:2012 (technicallyequivalent to ASTM D638-14). Modulus and strength measurements may bemade on the same test strip sample having a length of 80 mm, thicknessof 10 mm, and width of 4 mm. The testing temperature may be 23° C., andthe testing speeds may be 1 or 5 mm/min.

Flexural Modulus, Flexural Stress, and Flexural Elongation: Flexuralproperties may be tested according to ISO Test No. 178:2010 (technicallyequivalent to ASTM D790-10). This test may be performed on a 64 mmsupport span. Tests may be run on the center portions of uncut ISO 3167multi-purpose bars. The testing temperature may be 23° C. and thetesting speed may be 2 mm/min.

Notched Charpy Impact Strength: Charpy properties may be testedaccording to ISO Test No. ISO 179-1:2010) (technically equivalent toASTM D256-10, Method B). This test may be run using a Type 1 specimensize (length of 80 mm, width of 10 mm, and thickness of 4 mm). Whentesting the notched impact strength, the notch may be a Type A notch(0.25 mm base radius). Specimens may be cut from the center of amulti-purpose bar using a single tooth milling machine. The testingtemperature may be 23° C.

Dielectric Constant (“Dk”) and Dissipation Factor (“Df”): The dielectricconstant (or relative static permittivity) and dissipation factor aredetermined according to IEC 60250:1969. Such techniques are alsodescribed in Baker-Jarvis, et al., IEEE Trans. on Dielectric andElectrical Insulation, 5(4), p. 571 (1998) and Krupka, et al., Proc.7^(th) International Conference on Dielectric Materials: Measurementsand Applications, IEEE Conference Publication No. 430 (September 1996).More particularly, a plaque sample having a size of 80 mm×80 mm×1 mm wasinserted between two fixed dielectric resonators. The resonator measuresthe permittivity component in the plane of the specimen. Five (5)samples may be tested and the average value is recorded.

EXAMPLE 1

Sample 1 contains 100 wt. % LCP 1 for use in a melt-extruded substrate,which is is formed from 62% HNA, 2% HBA, 18% TA, and 18% BP. Samples areinjection molded into plaques (60 mm×60 mm) and tested for thermal andmechanical properties. The results are set forth below.

Sample 1 Dk @ 10 GHz 3.36 Df @ 10 GHz 0.0007 Tensile strength (MPa) 165Tensile modulus (MPa) 15,382 Tensile elongation (%) 1.2 Flexuralstrength (MPa) 215 Flexural modulus (MPa) 15,792 Charpy Notched (KJ/m²)17.3 DTUL at 1.8 MPa (° C.) 313.5 Melting Temperature (° C.) (1^(st)heat of DSC) 334

EXAMPLE 2

Sample 2 contains 100 wt. % LCP 2 for use in a melt-extruded substrate,which is is formed from 73% HNA and 27% HBA. Samples are injectionmolded into plaques (60 mm×60 mm) and tested for thermal and mechanicalproperties. The results are set forth below.

Sample 2 Dk @ 10 GHz 3.41 Df @ 10 GHz 0.001 Tensile strength (MPa) 140Tensile modulus (MPa) 6,883 Tensile elongation (%) 5.8 Flexural strength(MPa) 173 Flexural modulus (MPa) 8,873 Charpy Notched (KJ/m²) 78.8 DTULat 1.8 MPa (° C.) 199.6 Melting Temperature (° C.) (1^(st) heat of DSC)316

EXAMPLE 3

Sample 3 contains 100 wt. % LCP 3 for use in a melt-extruded substrate,which is is formed from 78% HNA, 2% HBA, 10% TA, and 10% BP. Samples areinjection molded into plaques (60 mm×60 mm) and tested for thermal andmechanical properties. The results are set forth below.

Sample 3 Dk @ 10 GHz 3.45 Df @ 10 GHz 0.0007 Tensile strength (MPa) 0.9Tensile modulus (MPa) 11,638 Tensile elongation (%) 0.9 Flexuralstrength (MPa) 167 Flexural modulus (MPa) 12,258 Charpy Notched (KJ/m²)1.9 DTUL at 1.8 MPa (° C.) 306.6 Melting Temperature (° C.) (1^(st) heatof DSC) 338

EXAMPLE 4

Sample 4 contains 100 wt. % LCP 4 for use in a melt-extruded substrate,which is is formed from 48% HNA, 2% HBA, 25% NDA, and 25% BP. Samplesare injection molded into plaques (60 mm×60 mm) and tested for thermaland mechanical properties. The results are set forth below.

Sample 4 Dk @ 10 GHz 3.48 Df @ 10 GHz 0.00064 Tensile strength (MPa) 160Tensile modulus (MPa) 7,332 Tensile elongation (%) 2.71 Flexuralstrength (MPa) 159 Flexural modulus (MPa) 7,678 Charpy Notched (KJ/m²)43.5 DTUL at 1.8 MPa (° C.) 234 Melting Temperature (° C.) (1^(st) heatof DSC) 329

EXAMPLE 5

Sample 5 contains 100 wt. % LCP 5 for use in a 5G system, which is isformed from 76% HNA and 24% HBA. Samples are injection molded intoplaques (60 mm×60 mm) and tested for thermal and mechanical properties.The results are set forth below.

Sample 5 Dk @ 10 GHz 3.41 Df @ 10 GHz 0.0010 Tensile strength (MPa) 160Tensile modulus (MPa) 8,720 Tensile elongation (%) 2.12 Flexuralstrength (MPa) 175 Flexural modulus (MPa) 8,926 Charpy Notched (KJ/m²)52.6 DTUL at 1.8 MPa (° C.) 208.1 Melting Temperature (° C.) (1^(st)heat of DSC) 325

EXAMPLE 6

Samples 6-7 are formed from various combinations of liquid crystallinepolymers (LCP 5 and LCP 1) and PTFE 1. PTFE 1 has a D50 particle size of4 μm and a D90 particle size of 15 μm. Compounding was performed usingan 18-mm single screw extruder. Parts are injection molded the samplesinto plaques (60 mm×60 mm).

6 7 LCP 5 75 — LCP 1 — 75 PTFE 1 25 25

Samples 6-7 were tested for thermal and mechanical properties. Theresults are set forth below in the table below.

Sample 6 7 Dielectric Constant (2 GHz) 3.18 3.17 Dissipation Factor (2GHz) 0.0010 0.0006 DTUL at 1.8 MPa (° C.) 201 306 Charpy Notched (kJ/m²)54 10 Tensile Strength (MPa) 127 — Tensile Modulus (MPa) 5,900 — TensileElongation (%) 3.5 — Flexural Strength (MPa) 135 137 Flexural Modulus(MPa) 7,000 14,000

These and other modifications and variations of the present inventionmay be practiced by those of ordinary skill in the art, withoutdeparting from the spirit and scope of the present invention. Inaddition, it should be understood that aspects of the variousembodiments may be interchanged both in whole or in part. Furthermore,those of ordinary skill in the art will appreciate that the foregoingdescription is by way of example only, and is not intended to limit theinvention so further described in such appended claims.

What is claimed is:
 1. A polymer composition comprising a liquidcrystalline polymer that contains repeating units derived fromnaphthenic hydroxycarboxylic and/or dicarboxylic acids in an amount ofabout 50 mol. % or more, wherein the polymer composition exhibits adielectric constant of about 4 or less and a dissipation factor of about0.05 or less at a frequency of 10 GHz, and further wherein the polymercomposition exhibits a tensile elongation of about 2% or more asdetermined at a temperature of about 23° C. in accordance with ISO TestNo. 527:2012.
 2. The polymer composition of claim 1, wherein the polymercomposition exhibits a tensile elongation of from about 4% to about 15%as determined at a temperature of about 23° C. in accordance with ISOTest No. 527:2012.
 3. The polymer composition of claim 1, wherein thepolymer composition exhibits a dielectric constant of about 3.6 or lessand a dissipation factor of about 0.002 or less at a frequency of 10GHz.
 4. The polymer composition of claim 1, wherein the polymercomposition has a melting temperature of from about 290° C. to about350° C.
 5. The polymer composition of claim 1, wherein the liquidcrystalline polymer contains repeating units derived from naphthenichydroxycarboxylic and/or dicarboxylic acids in an amount of about 70mol. % or more.
 6. The polymer composition of claim 1, wherein theliquid crystalline polymer contains repeating units derived from6-hydroxy-2-naphthoic acid in an amount of about 50 mol. % or more. 7.The polymer composition of claim 6, wherein the liquid crystallinepolymer contains 4-hydroxybenzoic acid in amount of from about 10 mol. %to bout 40 mol. %.
 8. The polymer composition of claim 6, wherein theliquid crystalline polymer contains repeating units derived from6-hydroxy-2-naphthoic acid in an amount of about 70 mol. % or more. 9.The polymer composition of claim 8, wherein the liquid crystallinepolymer contains 4-hydroxybenzoic acid in amount of from about 20 mol. %to about 30 mol. %.
 10. The polymer composition of claim 1, wherein theliquid crystalline polymer contains repeating units derived from6-hydroxy-2-naphthoic acid and 4-hydroxybenzoic acid in a molar ratio offrom about 0.1 to about
 40. 11. The polymer composition of claim 1,wherein the liquid crystalline polymer contains repeating units derivedfrom 6-hydroxy-2-naphthoic acid and 4-hydroxybenzoic acid in a molarratio of from about 1 to about
 5. 12. The polymer composition of claim1, wherein liquid crystalline polymers constitute 100 wt. % of thecomposition.
 13. The polymer composition of claim 1, wherein additivesconstitute from about 1 wt. % to about 60 wt. % of the polymercomposition and liquid crystalline polymers constitute from about 40 wt.% to about 99 wt. % of the polymer composition.
 14. A film comprisingthe polymer composition of claim
 1. 15. A film comprising a polymercomposition, wherein the polymer composition comprises a liquidcrystalline polymer that contains repeating units derived from6-hydroxy-2-naphthoic acid in an amount of about 70 mol. % or more,wherein the polymer composition exhibits a dielectric constant of about4 or less and a dissipation factor of about 0.05 or less at a frequencyof 10 GHz.
 16. The film of claim 15, wherein the polymer compositionexhibits a tensile elongation of about 2% or more as determined at atemperature of about 23° C. in accordance with ISO Test No. 527:2012.17. The film of claim 16, wherein the polymer composition exhibits atensile elongation of from about 4% to about 15% as determined at atemperature of about 23° C. in accordance with ISO Test No. 527:2012.18. The film of claim 15, wherein the polymer composition exhibits adielectric constant of about 3.6 or less and a dissipation factor ofabout 0.002 or less at a frequency of 10 GHz.
 19. The film of claim 15,wherein the polymer composition has a melting temperature of from about290° C. to about 350° C.
 20. The film of claim 15, wherein the liquidcrystalline polymer contains 4-hydroxybenzoic acid in amount of fromabout 20 mol. % to bout 30 mol. %.
 21. The film of claim 15, wherein theliquid crystalline polymer contains repeating units derived from6-hydroxy-2-naphthoic acid and 4-hydroxybenzoic acid in a molar ratio offrom about 0.1 to about
 40. 22. The film of claim 21, wherein the liquidcrystalline polymer contains repeating units derived from6-hydroxy-2-naphthoic acid and 4-hydroxybenzoic acid in a molar ratio offrom about 1 to about
 5. 23. The film of claim 15, wherein the film hasa thickness of from about 3 to about 100 micrometers.
 24. A laminate foruse in a circuit board comprising, the laminate comprising a conductivelayer and the film of claim
 15. 25. The laminate of claim 24, whereinthe film is positioned between two conductive layers.
 26. The laminateof claim 24, wherein the conductive layer comprises copper or an alloythereof.
 27. A circuit board comprising the laminate of claim
 24. 28. A5G antenna system comprising the circuit board of claim 27 and at leastone antenna element configured to transmit and receive 5G radiofrequency signals, wherein the antenna element is coupled to the circuitboard.